Monoazo dyestuffs



Patented Feb. 27, 1945 T" QFFICE Basil Jason Heywood, Arthur Howard Knight; and- Morvap Lapworth Blackley, Manchester, Eng-.- land; assignors to Imperial Chemical lndustriesg. 1 Limited; a corporation of GreatBritaiir No Drawing, Application May 27', 1943, Seriall filo. 488,750. In Great Britain June 29; 1942;

5 Claims; (01. 26.0.7206),

The p es ntinveatien: rela s. to. t e: m nui eta e i new: w terampl mo oaae fi mii suitable for dyeing and printing; acetateartificialsilk, wool, silk, tin-weightedsilk, and synthetic polyamide fibres such as; for example, nylon.

According to the; invention we make the said dyestuffs. by; coupling a, dlazotised p-aminm phenyl-hydroxyalkylx ether: sulphuric ester (also called, an aminophenyl. sulphatoalkyl ether) which may carry substituents. other than nuclear .sulphonic, carboxyl, or a cidylamino groups, with a, phenol capable of coupling and substituted in the 4.-position by: a hydrocarbon residue containing at least two and not. more.- than. eight carbon atoms, which hydrocarbon residueis. se: lected from the. groups alkyl, aralkyl, cycloalkyl and. aryl. V 4

Also according: to; the invention. we make. the. said dyestufts by couplin a. diazotised p-aminor phenyl-hydroxyalkyl: ether, which may carry substituents other than nuclear sulphonic, car-v boxyl. or acidrlamin eroupai with a phen l ca: pable of coupling and substituted in the 4-,p osi+v tion by a y rocarbo residue as al e dy defi and convertingthe; monoazo. compound s.o.-.ob,- tained into its sulphuric ester.

The conversion of: the monoazo .QQmpQundS referred to above into their sulphuric esters may be by treatment with sulphuric acid or other suitable known. agents. (see for xample. Die Methoden der Organischen; .Chemie, Houben, 1925, vol. 2, p. 67.3).

The new dyestufi s, in the form of their ammonium or alkali -.met al salts are soluble in water and have very good aifinity for acetate artificial silkL dyeing that material from a slig t y i n t al or s ight y a ka ine d ebath in non-phototropic yellow shades which have good fastness to'light and are dischargeable. They are also: very Suitable for'printing acetate artificial silk, yielding yel ow print of good light fastness and havin .a i h esi t n e in respect of sublimation or fmarking 013,3- iqr example during steaming.-

he new dre tuflis ma a s e used; a vanta eeusly for colour n wea silk v tin-we h d silk, and synt e ic: pnlwmfiefibres su h a fo example. nylon.

7 As az mponen s the e may be emplo ed for example:

n: m n phenylrfir rdrexyet et ulph r e ester, p-Aminophenyl y-hydroxypropyl, ether sulphuric ester, I ch ome4:am nophenrkp:hrdmxrflhy ether.

ulp r e er. 4 amino-2-methylphepyl g hydroxyethyl ether sulphuric ester, 1" -p-Aminophenoxwn-bptancl; sulphuric ester,

l amino-3-methylphenyl-p-hydroxyethy1 ether sulphuric ester, and i p-Aminophenyl-deltar-hydroxybutyl ether. su1= phuric ester The a oyel m eqnssqhents a e. b ainable y tr n th a lrji add th w 'r s lo 'd s aminophenyl hydr illgyl eth rs which latter m also. e u ed 8 male? e lteori n s accord n tothepresent ntion A enem es s=; .ta wh may e ployed according to the invention viee on; n-Ethy phenql n-n-Pmnxl hfliq -neBu lphe el p-i .--b1?4? l !Q-l. n-T t-em ehe l p-n-Hexylphenol p-Cyclohexylphenol p-I-Iydroxydiphenyl, and t. p-B nz phe q Y In in en ion illustra ed. w 9. m d. by he renewin et m e awhiq the Pa t re by wei h tame of sodium hydroxide. 39 parts ofanhydrous sodium carbonate and .8Qnarts o odium c l ride are added to the solution. This solution is coo ed to '1 (Jr-ammo it whil rile-stirr d, t e

' ab ve diazo sqlttiqn is raauallia lea When q uplin is comma? pa re .9? in ium chlo de ar aqdeqth e r am? is fi t red-strand driest ihi 'new e fi tenet Example 2 23.3 parts of p-aminophenyl-p-hydroxyethyl ether sulphuric ester are'diazotised as described in Example 1, and the diazo solution, cooled to by boiling 17.6 parts of p-cyclohexylphenol with 400 parts of water containing 4 parts of sodium hydroxide, cooling to -10 C. and adding 30 parts of anhydrous sodium carbonate and 80- parts of sodium chloride. When coupling is complete the new dyestufi is filtered ofi, washed with sodium chloride solution and dried. It forms a dull reddish yellow powder which dissolves in warm water to a reddish yellow solution and in concentrated sulphuric acid to a brownish red solution.

The new dyestufi dyes acetate artificial silk from a neutral bath containing sodium chloride or sodium sulphate in greenish yellow shades of very good fastness properties.

Example 3 23.3 parts of p-aminophenyl-p-hydroxyethyl ether sulphuric ester are diazotised as in Exam- I ple 1 and coupled to parts of p-tertiary-butylphenol by the method described in Example 2 in respect of p-cyclohexylphenol. The dyestufi so-obtained is filtered off, washed with 10% sodium chloride solution and dried.

It forms a yellow powder which dissolves in warm water to a reddish yellow solution and in concentrated sulphuric acid to a red-brown" solution.

The new dyestufi dyes acetate artificial silk in greenish yellow shades of very good iastness in respect of light and sublimation when applied from a neutral or slightly alkaline dyebath containing sodium chloride or sodium. sulphate. The dyeings ,are dischargeabler Example 4 2.3.3, parts of p-aminophenyl-p-hydroxyethyl ether sulphuric ester are diazotised as described in Example 1 and the diazo solution, cooled to 5-10 C., added to a stirred suspension prepared by boiling p-hydroxydiphenyl with 400 parts of water containing 4 parts of sodium hydroxide, cooling to 5-l0 C. and'adding parts of anhydrous sodium carbonate. After stirring the mixture until coupling is complete the dyestufi is filtered off, washed with a little water and dried at 40-50 C.

The new dyestufi forms a dull yellow powder which dissolves in warm water to an orange-yellow solution and in concentrated sulphuric acid to a dull scarlet solution.

The new dyestufi dyes acetate artificial silk from a neutral dyebath containing sodium chloride or sodium sulphate in greenish yellow shades, the dyeings having very good iastness to light and to sublimation, and good dischargeability.

iii

Example 5 The p-aminophenyl-B-hydroxyethyl ether sulphuric ester employed in Example 4 is replaced by 24.7 parts of p-aminophenyl-y-hydroxypropyl ether sulphuric ester. A dyestuff is obtained having similar properties of shade, iastness and dischargeability.

I 5-l0 C., added to a stirred suspension prepared 7 Example 6 23.3 parts of p-aminophenyl-p-hydroxyethyl ether sulphuric ester are diazotised as described in Example 1. The diazo solution is cooled to 510 C. and added to a stirred solution (at 5-l0 C.) of 18.4 parts of p-benzylphenol in 400 parts of water containing 4 parts of sodium hydroxide to which solution 30 parts of anhydrous sodium carbonate have been added. The

-in greenish yellow, non-phototropic shades of very-good fastness to light and sublimation and good dischargeability.

Example 7 24.7 partsof p-aminophenyl-y-hydroxypropyl ether sulphuric ester are employed instead of the p-aminophenyl-B-hydroxyethyl ether sulphuric ester in Example 6. A dyestufi having similar properties is obtained.

Example 8 24.7 parts of 4-amino-2-methylphenyl-p-hydroxyethyl ether sulphuric ester are diazotised by the method of Example 1. The diazo solutionis addedat 5-10 C. to a stirred suspension prepared by boiling 17 parts of p-hydroxydiphenyl in 400 parts of water containing 4 parts of sodium hydroxide, cooling to 5-10 C. and adding 30 parts of anhydrous sodium carbonate. When coupling is complete the new dyestufi is filtered ofi, washed with a little cold water and dried at 40-50 C.

The new dyestuff forms a light yellowish brown powder which dissolves in warm water to a reddish yellow solution and in concentrated sulphuric acid to a brownish red solution. It dyes acetate artificial silk from a neutral dyebath containing Glaubers salt or sodium chloride in greenish yellow shades, the dyeings having very good fastness to light and sublimation.

If 18.4 parts of p-benzylphenol are used instead of the 17 parts of p-hydroxydiphenyl employed above a dyestuff is obtained which forms an orange-brown powder. It dyes acetate artificial silk in yellow shades of good fastness to light and sublimation and good dischargeability.

Example 9 26.75 parts of 2-chloro-4-aminophenyl-'Bhydroxyethyl ether sulphuric ester are dissolved in 409 parts of water containing 4 parts of sodium hydroxide.- 35 parts of 36% hydrochloric acid are added followed by 6.9 parts of sodium nitrite. The solution of the diazo'is then cooled to 5-10 C. and gradually added to a stirred and similarly cooled solution of 15 parts of p-n-butylphenol in aqueous sodium hydroxide; chloride and carbonate prepared as described in Example 1. When coupling is complete the dyestufi is filtered off, washedwith a little cold water and dried at 40-50 C.

The new dyestuff forms a dull greenish yellow powder which dissolves in warm water to a reddish yellow solution and in concentrated sulphuric acid to a dull scarlet solution. It dyes acetate artificial silk from a neutral dyebath containing sodium chloride or Glaubers salt in greenish yellow shades'of good fastness to light and sublimation.

v Example 10v 24.7 parts of p-aminophenyl-'y-hydroxypropyl ether sulphuric ester are suspended in 300 parts of water containing 25 parts of 36% hydrochloric acid and diazotised at -10 C. by the addition of '7 parts. of sodium nitrite. The diazo solution is gradually added to a stirred solution at 510 C. of 15 parts of p-n-butylphenol in 400 parts of water containing 4 parts of sodium hydroxide and 30 parts of anhydrous sodium carbonate. Stirring is continued until coupling is complete. The new dyestufi is then filtered oil and dried at 40-50 C. It dyes acetate artificial silk from a neutral dyebath containing sodium chloride or Glaubers salt in non-phototropic greenish yellow shades of very good lightfastness.

Example 11 i v 15.3 parts of p-aminophenyl-;8-hydroxyethyl ether are dissolved in 400 parts of water and 25 parts of 36% hydrochloric acid. 6.9 parts of sodium nitrite are added. I

The diazo solution isadded at 510 C to a mixture prepared by stirring 13.6 parts of p-npropylphenol with 400 parts of water and 4 parts of sodium hydroxide till solution occurs, adding 21 parts of anhydrous sodium carbonate and cooling to 5-10. C. When coupling is complete the precipitated monoazo compound is filtered off, washed with water and dried.

The dried monoazo compound is powdered and added gradually (during about 1 hour) with stirring to 136 parts of 90% sulphuric acid. Stirring iscontinued for10-15 hours at -30 C.

The resulting solutionv is then poured into a'mix- Example 12 15.3 parts of. p-aminophenyl-;3-hydroxyethyl.

ether are diazotised as in Example 11. The diazo solution is added gradually to a cooled suspension prepared from 17 parts of p-hydroxydiphenyl as described in Example 4. Stirring is continued until coupling is complete. The precipitated monazo compound is filtered off, washed with water, dried at 40-50 C. and powdered. It is then converted to the sodium salt of its hydroxyethyl sulphuric ester by the method described in Example 11.

The new sulphuric ester dyestufi appears to be identical with the dyestufi of Example 4 and dyes acetate artificial silk from a dyebath containing sodium chloride or Glaubers salt in similar shades of greenish yellow, the dyeings having similarfastness properties and dischargeability.

If the 15.3 parts of p-aminophenyl-p-hydroxyethyl ether'employed above are replaced by 16.7 parts of p-aminophenyl-'y-hydroxypropyl ether a water-soluble dyestuff is obtained, believed identical with that of Example 5 which dyes acetate artificial silk in similar greenish yellow shades,

the dyeings having similar fastness properties and dischargeability.

We claim: 1. A monoazo dye represented by the formula:

wherein HO3SORO is a hydroxyalkyl ether sulfuric ester group having 2 to 4 carbons in which the oxygens are attached to different carbons of the alkylradical; X is one of the group consisting of hydrogen, methyl and chloro; and R is one of the group consisting of butyl, cyclohexyl, phenyl and benzyl.

2. A dye in accordance with claim 1 in which R is ethylene.

3. A monoazo dye represented by the formula:

4. A monoazo dye represented by the formula:

5. A monoazo dye represented by the formula:

BASIL JASON HEYWOOD. ARTHUR HOWARD KNIGHT. MORVAN LAPWORTH. 

